Photographic light-sensitive material suitable for silver-dye bleaching method

ABSTRACT

A LIGHT-SENSITIVE SILVER HALIDE EMULSION CONTAINING A DYE CAPABLE OF BEING BLEACHED IN THE SILVER DYE BLEACHING PROCESS AND AT LEAST ONE SENSITIZING DYE HAVING THE GENERAL FORMULA I   5-(5-((-Z-N(-R)-(CH=CH)(N-1)-)&gt;C=(CH-C(-R4))D=),4-(O=),   3-R2-THIAZOLIDIN-2-YLIDENE),2-((-Z1-N(-R1)=(CH-CH)(M-1)=)   &gt;C-C(-R&#39;&#39;)=),4-(O=),3-R3-THIAZOLIDINE (X(-))(P-1)   WHEREIN R, R1, R2 AND R3 EACH IS SELECTED FROM THE GROUP CONSISTING OF AN ALKYL, A SUBSTITUTED ALKYL, AN ALLYL, AN ARALKYL, A SUBSTITUTED ARALKYL AND AN ARYL GROUP, WHEREIN R&#39;&#39; IS SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM, AN ARKYL GROUP, A SUBSTITUTED ALKYL GROUP, AND AN ALIPHATIC CHAIN TO BE COMBINED WITH THE N OF THE HETEROCYCLIC RING CONTAINING ZI, WHEREIN R4 IS SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM, AN ALKYL AND AN ARYL GROUP, WHEREIN M,N, AND P ARE 1 OR 2, AND D REPRESENTS 0, 1 OR 2, WHEREIN X REPRESENTS AN ANION, WHEREIN AN INTRAMOLECULAR SALT IS FORMED WHEN P=I, AND WHEREIN Z AND Z1 EACH IS THE NON-METALLIC ATOMIC GROUP NECESSARY TO COMPLETE A 5- OR 6-MEMBERED HETEROCYCLIC RING, IS DISCLOSED. THE EMULSION CAN BE SUPER-SENSITIZED BY THE ADDITION OF A SUPERSENSITIZING DYE TO THE EMULSION.

r 3,728,125 Ice Patented Apr. 17, 1973 method of color forming typeusing a multi-layer photo- 3,728,l25 graphic material. For example, sucha material comprises PHOTUGRAPHIC LIGHT-SENSIT VE MATERIAL on a supportmember a red-sensitive layer containing a FOR MINER-DYE BLEACHING cyandye, a green-sensitive layer containing a magenta Keisuke Shiba, MasanaoHinata, Malroto Yoshida, 5 Y 9Y layer Capable decreasing the ShinichiImai, Akita Sam, and Shigem Watanabe, trinsic sensitivity of the layersunder the filter layer and Kamgawa, Japan assignors to Fuji Photo FilmCo a blue-sensiuve layer containing a yellow dye as an upper- Ltd.,Kanagawa, Japan most y No Drawing. Filed Aug. 20, 1970, Ser. No. 65,714One of the disadvantages of the silver-dye bleaching Claims priority,applicah'on Japan, Aug. 20, 1969, 10 method is that the light-sensitivespeed of a dyed photo- I t g/oGStEMI/IO graphic layer is considerablydecreased, because the Us. Cl 96-39 14 Claims maximum wavelength ofsensitivity substantially coin cides with the adsorption maximumwavelength of the dye. The sensitivity of the light-sensitive layer inthe ABSTRACT OF THE DEC 15 silver-dye bleaching method is lower thanthat of other A light-sensitive silver halide emulsion containing a P Pmeth0d$- herefore, one of large difdye capable of being bleached in thesilver dye bleaching ficllltlcs Present With h y f h h method 15 processand at least one sensitizing dye having the genp p r a l y r havingsuflicient sensitivity. eralFormulaI In making silver halide emulsions,a sensitizing dye 0 $2 0 1E3 --Z R4 ih--N iiN I "Z1 R-n't-on=o11).-1-b(=on-h)d=d h=c ti=o-o' =on-on)m-i=i rni s s it (Km-1 [I]wherein R, R R and R each is selected from the group is added to silverhalide thus to enlarge the spectral region consisting of an alkyl, asubstituted alkyl, an allyl, an of sensitivity of the silver halideemulsion and to sensiaralkyl, a substituted aralkyl and an aryl group;wherein tize optically. The sensitizing dye used in a light-sensitive Ris selected from the group consisting of a hydrogen material for thesilver-dye bleaching method must satisfy atom, an alkyl group, asubstituted alkyl group, and an certain necessary conditions. Thesensitizing dye should aliphatic chain to be combined with the N of theheteronot have adverse influences upon the sensitivity and the cyclicring containing Z wherein R, is selected from the stability of theemulsion, in particular, during storage. group consisting of a hydrogenatom, an alkyl and an Furthermore, the sensitizing dye should not resultin color aryl group; wherein m, n, and p are 1 or 2, and a repremainingafter processing of the photographic material. resents O, 1 or 2;wherein X represents an anion, wherein Furthermore, the sensitizing dyeShould be adsorbed a intramolecular salt i f d hen 1:1; and wherein faston silver halide grains not so as to be substituted by Z and Z each isthe non-metallic atomic group necessary a dye suitable for the slver-dye bleaching method. Otherto complete a 5- or 6-memberedheterocyclic ring, is dis wise, the sensitizing action is decreased bythe presence of closed. The emulsion can be super-sensitized by theadthe y sulta'hle t the Silva-dye bleaching methodditi f upersensifizingdye to th l i Many of the sensitizing dyes used hitherto in silverhalide materials are not suitable for the silver-dye bleaching method.BACKGROUND OF THE INVENTION For example, the basic cyanine tends to bedesorbed from the silver halide grains by a dye having a sull f th tonFleld o e mven 1 fonate group, suitable for the silver-dye bleachingmeth- ThlS lnvefltltfh re1atet0 the spfictfal FQnsltlZatlOn od. Betainecyanines may be used as the sensitizing dye photographic l ght-sens tivelayer containing a dye suitfor a photographic layer in the Si1ver dyebleaching a'ble fOT 11Se Wlth the sllvef-dye bleachlng methodmethod, butoften a slight coloring is retained therein.

It is an object of this invention to provide a sensitizing (2)Descnptlon of the pnor art dye available for a silver halide emulsionused in the It is well known that monoor multi-colored photosilve adyebl hi h d,

graphic images are obtained y the ye bleaching It is another object ofthis invention provide a method based 011 breakage of a y depending onthe photographic material constituted of at least one lightqllflntity ofdeveloped Silver- In this method, an image is sensitive silver halideemulsion layer optically sensitized recorded iirstly as a silver imageon a light-sensitive layer d containing a dye, it bl f th silver-dye blhcolored uniformly with a dye using ordinary exposing i h d, anddeveloping methods. Then the dye present in this other obj t n bapparent f o the following layer is decomposed in proportion to thequantity of scription d examples,

silver present sectionally by the silver-dye bleaching bath.

Thereafter, the silver is removed to retain a dye layer SUMMARY OF THEINVENTION having a reverse gradation to that of the original silver Aphotographic light-sensitive layer suitable for the image. In thesilver-dye belaching method also, as is well silver-dye bleaching methodand having an extraordiknown, the use of a multi-layer material havingthree narily high sensitivity is prepared by adding to a silver or morecomponent color layers of sensitivity-differing halide emulsioncontaining a dye suitable for the silver spectrum regions isadvantageous to obtain a multidye bleaching method, a sensitizing dye,as a sensitizer, colored photograph as in the case of the colordeveloping represented by the following generally Formula I:

I i i /'Z"""-\ 1? l I I R" N(""GH=OH)11- -O (=CHO)n=o o=o-o (=oH-oH =NRwherein R, R R and R each represents alkyl, substituted alkyl, allyl,aralkyl, substituted aralkyl and aryl groups; wherein R represents ahydrogen atom, an alkyl group, a substituted alkyl group or an aliphaticchain to be combined with N in the heterocyclic ring containing Zwherein R represents a hydrogen atom, an alkyl group or an aryl group;wherein m, n and p represent respectively 1 or 2, and d represents 0, 1or 2; wherein X represents an anion; and wherein Z and Z each representsthe non-metallic atom groups necessary to complete a 5- or 6-memberedheterocyclic ring. An intramolecular salt is for-med when p=1.

R, R R and R in the general Formula I can be, for example, a methyl, anethyl, a propyl, a fi-hydroxyethyl, a B-acetoxyethyl, a sulfato ethyl, acarboxymethyl, a fl-carboxyethyl, a 'y-carboxypropyl, a fi-sulfoethyl, a'ysulfopropyl, a a-sulfobutyl, a vinyl-methyl, a benzyl, a phenethyl, ap-carboxbenzyl, a p-sulfophenethyl and a phenyl group.

R in the general Formula I can be, for example, a methyl, an ethyl or aphenyl group. The substituted alkyl group R in the general Formula I canbe, for example, a p-hydroxyethyl, a fl-acetoxyethyl or a B- aminoethylgroup.

X in the general Formula I can be, for example, a chloride ion, abromide ion, a perchlorate ion, a p-toluenesulfonate ion, abenzeuesulfonate ion, an ethylsulfate ion or a methylsulfate ion.

Examples of the heterocyclic ring containing Z or Z in the generalFormula I are thiazoles, such as thiazole and thiazoles having a methylor a phenyl group in the ring; benzothiazoles, such as benzothiazole andbenzothiazoles having nucleus substitutents such as a halogen atom,alkyl, alkoxy, and phenyl groups in the benzene ring; naphthothiazoles,such as u-naphthothiazole, flnaphthothiazole, tetrahydronaphthothiazoleand naphthothiazoles having nucleus substituents such as an alkoxy groupin any of the benzene rings; oxazoles, such as those having substituentssuch as alkyl and phenyl groups in the ring, benzoxazoles, such asbenzoxazole and benzoxazoles having nucleus substituents such as ahalogen atom, methyl, ethyl, ethoxy, hydroxyl and phenyl groups in thebenzene ring; naphthoxazoles, such as ot-naphthoxazole, andp-naphthoxazole; selenazoles, such as 4-methylselenazole, and4-phenylselenazole; benzoselenazoles, such as 5 chlorobenzoselenazole, 5methylbenzoselenazole, 5- methoxybenzoselenazole, andS-hydroxybenzoselenazole; naphthoselenazoles, such asa-naphthoselenazole and B- naphthoselenazole; thiazolines, such asthiazoline and 4- methylthiazoline; 2-quinolines, such as Z-quinolineand Z-quinolines having nucleus substituents (exclusive of the2-position) such as a halogen atom, methyl, methoxy and hydroxyl groupsin any of the benzene rings; 4-quinolines, such as 4-quinoline and4-quinolines having nucleus substituents (exclusive of the 4-position)such as methyl and methoxy groups in any of the benzene rings;benzimidazoles, such as 1,3-diethylbenzimidazole,1,3-diethyl-S-chlorobenzimidazole and1,3-diethyl-5,6-dichlorobenzimidazole; 3,3'-dialkylindolenines, such as3,3'-dimethylindolenine,

3,3',5-triethylindolenine and 3,3'-trimethylindolenine;

2-pyrridine, such as 2-pyridine and 2-pyridines having nucleussubstituents (exclusive of the 2-position), such as a methyl group; and4-pyridines, such as 4-pyridine.

The sensitizing dye represented by the general Formula I I is a dyehaving four hetero radicals wherein two ketomethylene radicals aredirectly bonded, which can sensitize a silver halide emulsion stronglyin the coexistence with the dye used in the silver-dye bleaching method.Since it gives a more excellent sensitivity even in the case of a smallquantity of the dye added per g-mole of silver halide in comparison withthe conventional basic cyanine dyes, any photographic layer containingit is substantially freed from color remaining after processing.

The sensitizing dye represented by the general Formula I can favorablysensitize an emulsion used in the silverdye bleaching method, containinga dye suitable for the silver-dye bleaching method, without any aid, butsupersensitization of the sensitizing dye by a compound represented bythe following general Formulae H or III is preferred.

Compound II has the general formula shown below:

N N m-f TNH-A-NHW TR Y N N o I'is [II] In this formula, Y represents=CH- or =N-; R R R and R each represents a hydrogen atom, a hydroxylgroup, an alkoxyl group, an aryloxyl group, a substituted aryloxylgroup, such as a phenoxyl, an o-toloxyl or a p-sulfophenoxyl group, ahalogen atom, such as a chlorine or a bromine atom, a heterocyclicnucleus such as morpholinyl or piperidyl, an alkylthio group such as amethylthio or an ethylthio group, a heterocyclic thio group such as abenzothiazylthio group, an arylthio group, an unsubstituted or asubstituted alkylamino group, such as a methylamino, an ethylamino, apropylamino, a dimethylamino, a diethylamino, a dodecylamino, acyclohexylamino, a fi-hydroxyethylamino, a di-B-hydroxyethylamino or a,B-sulfoethylamino group, an arylamino group or a substituted arylaminogroup such as an anilino, an o-sulfoanilino, a m-sulfoanilino, ap-sufoanilino, an oanisilamino, a m-anisilamino, a p-anisilamino, ano-toluidino, a m-toluidino, a p-toluidino, an o-carboxyanilino, am-carboxyanilino, a p-carboxyanilino, a hydroxyanilino, a naphthylamino,or a. sulfonaphthylamino group, a heterocyclic amino group, such as a2-benzothiazoleamino or a 2-pyridylamino group, or an aryl group, suchas a phenyl group; and A represents A or A shown as follows and, inparticular, at least one of R R R and R representing a substituentcontaining a SO M group when A is A OONHQGEEOHQNHCO-Ql A can he:

and

Compound III has the general formula shown below:

[III] In this formula, R represents an acylamino group, such as anacetamide, a sulfobenzamide, a 4-methoxy-3-sulfobenzamide, a2-ethoxybenzamide, a 2,4-diethoxybenz amide, a p-toluylamino, a4-methyl-Z-methoxybenzamide, a l-naphthylamino, a Z-naphthylamino, a2,4-dimethoxybenzamide, a 2-phenylbenzamide, or a 2-thienylbenzamidegroup, or a sulfo group; R represents an acylamino group, such asdefined above for R and R represents a hydrogen atom or a sulfo group.The compound having the general Formula III has at least one sulfogroup.

The sensitizing dye represented by the general Formula I is used morefavorably through supersensitization with a Novolak type condensate of apolyhydroxybenzene and formaldehyde. The term polyhydroxybenzene isintended to cover substituted benzenes having from 1 to 3 hydroxylgroups on the benzene nucleus. The Novolak type condensate of thepolyhydroxybenzene and formaldehyde will hereinafter be referred to asthe Formalin condensate.

The polyhydroxybenzenes are represented by the following generalFormulae IVa, IVb, IVc, IVd:

wherein R and R each represents -OH, 0M, '-OR14: 'NH2, -NHR14, N(R14)2,and -NI-INHR with R representing an alkyl group of from 1 to 8 carbonatoms, an aryl group or an aralkyl group; M represents an alkali metalor an alkaline earth metal; X represents an Ol-I group or halogen atom;X; represents a halogen atom; n n n and n each reprno- C 118 N/ tiJzHs Se H3 Ha resents l, 2, or 3, except that n and n are equal to 3 at thesame time.

The sensitizing dye of the invention, represented by the general FormulaI, is described in F. M. I-Iamer, Cyanine Dyes and Related CompoundsThereof, Sect. 15, p. 671, Interscience Publishers (1964).

Some of the compounds represented by the general Formula II arementioned, for example, in US. Pats. 2,171,- 427, 2,660,578 and2,595,030. One method of synthesis of the Formalin condensate isillustrated as follows.

The condensate of the polyhydroxybenzene can be synthesized according tothe conventional synthesis method for phenol-formaldehyde resins of theNovolak type [(for example, as described in W. R. Sorenson, T. W.Campbell, Preparative Methods of Polymerchernistry, John Wiley and Sons,Inc. (1961)]. The polysubstituted hydroxybenzene is dispersed in water,heated after concentrated hydrochloric acid and 37% Formalin are addedand held at C. for 30 minutes to 1 hour with agitation. Then, ifnecessary, hydrochloric acid is added further and the heating withagitation is continued. After the reaction, the reaction product isremoved into cold water and the resultant precipitate can be purified.More specifically, 415 parts of p-hydroxybenzoic acid is dispersed in1,000 parts of water with vigorous agitation, to which 25 parts of 35%or more concentrated hydrochloric acid and 245 parts of 37% Formalin areadded. Then the reaction mixture is heated at 100 C. with agitation andheld for 30 minutes as it is, to which 20 parts of concentratedhydrochloric acid is additionally added followed by reaction for 30minutes. At this point, 20 parts of concentrated hydrochloric acid isfurther added thereto and the stirring is continued until the reactionsolution becomes cloudy. After about 1 hour and 30 minutes, the stirringis stopped and the mixture is removed into 3,000 parts of cold Waterwith stirring. The resulting precipitate is filtered, redissolved in1,000 parts of methanol as it is not dried, and then precipitated withWater. The reaction product is filtered and dried to obtain the product.Other condensates can readily be obtained by using otherpolyhydroxybenzenes in place of the p-hydroxybenzoic acid in theabovedescribed method. The condensation unit (i.e., the degree ofpolymerization) of the condensate obtained by the above described methodis from 2 to 10 as with usual Novolak resins.

For the purpose of the invention, condensates having a condensation unitof from 2 to 10, preferably having a condensation unit of from 2 to 5and a molecular weight of from 300 to 800 are suitable.

Examples of the sensitizing dye used in the invention are given asfollows, but without limiting the invention.

The sensitizing dye represented by the general Formula I is added to aphotographic layer used in the silver-dye bleaching method With a dyesuitable for the silver-dye bleaching method. In particular, thesensitizing dye is preferably added to an emulsion before coating, andwashed with water, before an azo dye is added.

Methods of adding a sensitizing dye to a photographic emulsion are wellknown in the field of making photographic emulsions. Generally, the dyeis added to photographic emulsions in the form of a solution in water oran organic solvent, such as methanol or ethanol.

Suitable emulsions for use in this invention are silver halide, such assilver chloride, silver bromide, silver iodobromide, silverchlorobromide or silver chloroiodobromide CO-NH OH 10 emulsions. Theusual gelatino-silver halide emulsion is used in the invention, butcellulose derivatives and resinous materials which do not disturblight-sensitive materials can be used in place of the gelatin.

The photographic emulsion used in the invention can have conventionaladditives such as chemical sensitizers, fog inhibitors, stabilizers,hardeners, coating aids, plasticizers, development accelerators and airfog inhibitors.

The photographic emulsion can be coated onto a suitable support, such asa glass, a cellulose derivative film, a synthetic resin film, alaminated paper or a synthetic paper in any conventional manner.

The dye used in combination with the sensitizing dye represented by thegeneral Formula I is any dye used conventionally in the silver-dyebleaching method, preferably one containing a phenolic hydroxyl group ora sulfonate group. Suitable dyes are described in Japanese patentpublications 10,280/61, 9,587,/64 and 25,768/ 64, and in U.S. Pats.3,211,554, 3,223,527, 3,264,109, 3,454,402, 3,178,291, 3,385,706,3,455,695, 3,259,498, 3,244,525, 3,304,181, 3,322,543, 3,210,190 and3,454,401. Suitable dyes are, for example:

SO H 00 NH HO 5 so NH 2 a (I!) (I? (I) 311 a =N NH=c--NH-o-NHd-HN N=N OHHO 83011 c Q-cm o-N N ou=o 61 Q CH3 Hols SIOaH =NQ-Nll-ji-HN Hg 43H:

CIQCO-NH H H300 on H018 303E CH:

mc-oo-mvQo 0-NH on H800 on H0; S0311 CH3 H035 @0011: OH OCH; on NHOOQN=N N=N NH,

Hols SOaH H Hols 03H 11 Q-CO-NH on molo 011 N=N N=N OaH 0211, g

Q-CO-NH on moo 0H N=N N=N H058 01H CH: Hots R-NH 011 cm on;

Hols son; mo om Hols Hz (3H1 with R being a p-tolpenesulfone group or a4-acetylaminobenzoyl group,

N=NN=N 30311 on, H088 soar:

with R being a benzoyl, a 4-acetylaminobenzoyl or a 4-benzoylaminobenzyl group.

The following examples are given to further illustrate the inventionwithout limiting the scope of the invention.

EXAMPLE 1 HOsS the coated photographic layer was exposed through a stepwedge of blue light (Latten Filter No. 478) and red light (Fuji FilterNo. 7), developed and fixed. The development was carried out with thedeveloper having the composition shown in Table 1 at 20 C. for 2minutes.

The results obtained are shown in Table 2 wherein a larger value means ahigher sensitivity.

45 TABLE 1 G. N-methyl-p-aminophenyl sulfate 3.1 Sodium Sulfite 45Hydroquinone 12 50 Sodium carbonate (anhydrous) 67.5 Potassium bromide1.9

Water to 1000 ml.

Structural formula of dye used 0 OHN 0H 0 OH: OH

H015 SOaH CH:

Structural formula of sensitizing dye used Ia(for comparison) I-b(forcomparison) r M m S w H a W 0 4 m 0 w a a a S IO TABLE 2 The thus coatedphotographic layer of the samples was exposed through a step wedge andsub jected to the folsensitizing dye I-b (for comparison)..

(3) Fixing-J minutes:

Crystalline sodium thiosulfate g 200 15 16 (7) Dye bleaching-15 minutes:1 2 The results obtained are showed in Table 3 below:

Thiourea m 8 Potassium bromide g 18 TABLE 3 Thiourea 2 282-amino-3-hydroxyphenazine mg 3 5 Concentrated hydrochloric acid ml 200(re Water to 1,000 m1. sensitizing dye Supersensltizer sensitivity) (8)Water washing-5 minutes. (950)! 202 (9) Bleaching fixing-1O minutes:i133 Tetrasodium ethylenediaminetetraacetate g 26 10 2.38 Anhydroussodium carbonate g 24 23%? Ferric chloride g 5- Anhydrous sodium sulfiteg 13 1 Crystalline sodium thiosulfate g 200 Water to g 15 hulxlilligrams supersensitizer per g.-mol silver (10) Water washmg-2ommutes' C iidensate of pehlorophenol and formalde- Structural formula ofdye used Wk (5700)- Structural formula of supersensitizer used II-l HNN\ HN -CH=CH NH /N NH- @3 U OaNB OaNa *HQ Q 2 3.1% N CH=CHQNH lei-Q i it031% g OaNa @jOgNH OSN: H=C HQNHQO 6 NaOzS SOzNa 0 o o o Q HNUS Nil-8QStructural formula of sensitized dye used (1-1, 1-2, 1-3, and 1-4, asshown in Example 1).

anilino group, an o-anisilamino group, a m-anisilamino group, ap-anisilamino group, an o-toluidino group, a mtoluidino group, ap-toluidino group, a p carboxyaniliho group, a hydroxyanilino group, anaphthylamino group,

and a sulfonaphthylamino group, a heterocyclic amino group selected fromthe group consisting of a 2-benzowherein R, R R and R each is selectedfrom the group consisting of an alkyl group, an allyl group, an aralkylgroup, an aryl group, a substituted alkyl group wherein said substituentis selected from the group consisting of hydroxy, acetoxy, sulfato,carboxy, sulfo and vinyl, and a substituted aralkyl group wherein saidsubstituent is selected from the group consisting of sulfo and, carboxy,and wherein R is selected from the group consisting of a hydrogen atom,an alkyl group, a hydroxy alkyl group, an acetoxy alkyl group, and anamino alkyl group, and an aliphatic chain to be combined with the N ofthe heterocyclic ring containing Z wherein R is selected from the groupconsisting of a hydrogen atom; an alkyl group, and an aryl group;wherein m, n, and p are l or'2, and d represents 0, l or 2; wherein Xrepresents an anion wherein an intramolecular salt is formed when 11:1;and wherein Z and Z is selected from the group consisting of thethiazoles, benzothiazoles, naphthothiazoles, oxazoles, benzoxazoles,naphthoxazoles, selenazoles, benzoselenazoles, naphthoselenazoles,thiazolines, Z-quinolines, 4-quinolines, benzimidazoles,3,3'-dialkylindolenines, Z-pyridines and 4-pyridines.

2. The light-sensitive silver halide emulsion as claimed in claim 1,whrein R, R R and R are selected from the group consisting of methyl,ethyl, propyl, fl-hydroxyethyl, p-acetoxyethyl, sulfatoethyl,carboxymethyl, flcarboxyethyl, -carboxypropyl, fl-sulfoethyl,'y-sulfopropyl, 6-su1fobutyl, vinylmethyl, benzyl, phenethyl,pcarboxybenzyl, p-sulfophenethyl, and phenyl groups; wherein thesubstituted alkyl group in R is selected from the group consisting of afi-hydroxyethyl, aT'B-acetoxyethyl and a fl-aminoethyl group; andwherein the heterocyclic ring containing Z or Z; is selected from thegroup consisting of the thiazoles, benzothiazoles, ,naphthothiazoles,oxazoles, benzoxazoles, naphthoxazoles, selenazoles, benzoselenazoles,naphthoselenazoles, 't'hiazolines, 2-c1uinolines, 4-quinolines,benzimidazoles, 3',3-dialkylindolenines, 2-pyridines and 4pyridines.

-3. A supersensitizing photographic emulsion wherein the light sensitivesilver halide emulsion of claim 1 contains additionally at least onecompound having the following general Formula II wherein Y represents=CH or =N-; wherein R R R, and R each is selected from the groupconsisting of a hydrogen atom, a hydroxyl group, an alkoxyl group, anaryloxyl group, a substituted aryloxyl group selected from the groupconsisting of an o-toloxyl group and a psulfophenoxyl group, a halogenatom, a heterocyclic nucleus selected from the group consisting of amorpholinyl group and a piperidyl group, an alkyl thio group, abenzothiazylthio group, an aryl thio group, an alkyl amino group, asubstituted alkyl amino group selected from the group consisting of aB-hydroxyethylamino group, a di-fi-hydroxyethylamino group, and aB-sulfoethylamino group, an arylamino group, a substituted arylaminogroup selected from the group consisting of an osulfoanilino group, am-sulfoanilino group, a p-sulfoand thiazoleamino group and aZ-pyridylamino group and an aryl group; and wherein A is selected fromthe group consisting of A and A wherein A is selected from the groupconsisting of 803M MO S $03M $03M SOaM 303M wherein A is selected fromthe group consisting of and wherein at least one of R R R and R is asubstituent containing a SO M group when A is A 4. Asupersensitized"photographic emulsion wherein the light-sensitive silverhalide emulsion of claim 1 contains additionally at least one compoundhaving the following general Formula III III u wherein R is selectedfrom the group consisting of an acylamino group and ai sulfo group;wherein R is an acylamino group; and wherein R is selected from thegroup consisting of a hydrogen atom and a sulfo group;

and wherein said compound has at least one sulfo group.

the light-sensitive silver halide emulsion of claim 1 con tainsadditionally a condensate of a polyhydroxy benzene and formaldehyde.

19 20 7. The supersensitized photographic emulsion as densation unit offrom 2 to 5 and a molecular weight of claimed in claim 6, wherein theformalin condensate is from 300 to 800. a Novola-k type condensate offormaldehyde and a poly- 9. The light-sensitive silver halide emulsionas claimed hydroxybenzene having a formula selected from the in claim 1wherein the dye capable of being bleached out group consisting offormulas in the silver dye bleaching process is (0H)n1 r (0H)n2 Q-CONH0]?! onto 0H [IVa] [IVb] I 10 N=N N=N I l 802R" H033 scan CH3 03H 10 1 lI 15 10. The light-sensitive silver halide emulsion as claimed in claim1, wherein the dye capable of being bleached out X1 CH2 in the silverdye bleaching process is wherein R and R each is selected from the groupcon- 11. The light-sensitive silver halide emulsion as sisting of -OH,OM, OR NH NHR claimed in claim 1, wherein the dye capable of being --N(R-NHN H and NHNHR wherein R bleached out in the silver dye bleachingprocess is -SO H 0:011;

is selected from the group consisting of an alkyl group 12. Thelight-sensitive silver halide emulsion as having from 1 to 8 carbonatoms, an aryl group and an claimed in claim 1, wherein the dye capableof being aralkyl group; wherein M is selected from the group bleachedout in the silver dye bleaching process is 43011111 (IJH H300 (13H H038SOzH 6-011:

Hogs

consisting of an alkali metal and an alkaline earth metal; 13. -Aphotographic light-sensitive element comprising wherein X is selectedfrom the group consisting of an a support having thereon at least onelayer containing the --OH and a halogen atom; wherein X is a halogenatom; 5 light-sensitive silver halide emulsion as claimed in claim 1.wherein n 11 n and n1 each are 1, 2 or 3, except that 14. Thelight-sensitive silver halide emulsion as claimed n and n are equal to 3at the same time. in claim 1, wherein the dye capable of being bleached8. The supersensitized photographic emulsion as out in the silver dyebleaching process is selected from claimed in claim 7, wherein thecondensate has a com the group consisting of SOBH bCHs SOaH Q-OCHN 110011, OH sumo-Q, NH:

H0 5 SOaH HzCO HOaS SOIH H 0 3S and CONE 0H H300 I OH HOaB 0 H (L-CH:H038 References Cited UNITED STATES PATENTS 3,401,404 9/1968 Seidel eta1. 96-99 3,520,693 7/1970 Gotze et a1. 96-99 3,178,285 4/1965 Anderauet a1. 9673 3,582,348 6/1971 Haseltine et a1. 96-141 J. TRAVIS BROWN,Primary Examiner US. Cl. X.R. 96-73, 123, 128

